CN104017042A - Separation purification method for 7-dehydrocholesterol - Google Patents
Separation purification method for 7-dehydrocholesterol Download PDFInfo
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- CN104017042A CN104017042A CN201410210759.2A CN201410210759A CN104017042A CN 104017042 A CN104017042 A CN 104017042A CN 201410210759 A CN201410210759 A CN 201410210759A CN 104017042 A CN104017042 A CN 104017042A
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Abstract
The invention discloses a separation purification method for 7-dehydrocholesterol. The method comprises: firstly dissolving a 7-dehydrocholesterol fermentation material obtained in a biosynthetic process of cholesterol in solvents of hexane and water, fully stirring, filtering, standing for layering, so as to obtain a water phase and an organic phase; distilling the organic phase to remove hexane, then adding methanol, heating with stirring, after stirring is finished, performing pumping filtration, so as to obtain a filtrate and a filter residue; reducing the temperature of the filtrate for crystallization, and performing pumping filtration, so as to obtain cholesterol; adding a mixture of hexane and methanol in to the filter residue, heating with stirring, after full stirring is finished, performing pressure-reduction distillation, after distillation is performed, performing temperature-reduction crystallization and pumping filtration on the residue, so as to obtain a high-purity product 7-dehydrocholesterol. The method is capable of effectively separating and purifying high-purity 7-dehydrocholesterol from a product 7-dehydrocholesterol fermentation material, and also effectively recovering unconverted cholesterol and utilizing cholesterol for once-more feeding, so that the raw material is utilized to a relatively high degree, and accords with demands of current sustainable economic development.
Description
Technical field
The present invention relates to a kind of organic method of purification, particularly relate to a kind of separation purification method of 7-DHC.
Background technology
7-DHC (7-DHC) is a kind of steroid material.Be present in the sebiferous gland and secretory product thereof in animal skin.7-DHC is white crystalline powder or light yellow crystalline powder, and its molecular formula is C
27h
44o, also claims vitamins D
3former.In human body, can be transformed by cholesterol.It is stored in subcutaneous, under daylight or uviolizing, can change vitamins D into
3, there is the biological activity that regulates calcium, phosphorus metabolism.Therefore, children's get sun more or carry out according to plan uviolizing can preventing child rickets.
7-DHC main application is: it is synthesis of vitamin d
3important intermediate, also as the additive in skin care sun care preparations.
At present, the preparation method of 7-DHC is generally: the one, and 7-DHC is separation and Extraction in pigskin; The 2nd, utilize cholesterol to obtain through acidylate, oxidation, hydrazone, de-hydrazone, saponification, a kind of medicine intermediate that 7-DHC saponification reaction is synthetic.Utilizing the synthetic 7-DHC of cholesterol bio-transformation is the synthetic method of having succeeded in developing at present, but does not carry out large-scale industrial production.
But, utilize cholesterol to carry out in bio-transformation synthetic method, the product obtaining is 7-DHC fermented material, contains microzyme culture medium, unconverted raw material cholesterol and 7-DHC in the 7-DHC fermented material obtaining.Therefore, want to obtain the 7-DHC product that purity is higher, need to study a kind of from product 7-DHC fermented material the effective method of separating-purifying 7-DHC.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of from product 7-DHC fermented material the effective method of separating-purifying 7-DHC, the invention provides a kind of separation purification method of 7-DHC.Utilize technical solution of the present invention can be effectively from product 7-DHC fermented material separating-purifying go out 7-DHC, and can the unconverted cholesterol of efficient recovery, it is reused for again and feeds intake.Utilize technical solution of the present invention can access the 7-DHC product that purity is greater than 98%.
In order to address the above problem, the technical scheme that the present invention takes is:
The invention provides a kind of separation purification method of 7-DHC, described separation purification method comprises the following steps:
A, utilize existing cholesterol bio-transformation synthetic method to obtain 7-DHC fermented material in contain microzyme culture medium, unconverted raw material cholesterol and 7-DHC; First gained 7-DHC fermented material is dissolved in solvent normal hexane, and adds water, the add-on of described normal hexane and water is 5～10 times of 7-DHC fermented material volume, stirs at normal temperatures 1～1.5h after adding normal hexane and water; After stirring, filter, remove water insoluble and impurity normal hexane; Gained filtrate stratification, then carries out separatory, separates water and organic phase; After separatory, adopt normal hexane washing gained water 2～3 times, merge organic phase;
B, the organic phase that step a is obtained are distilled, and except desolventizing normal hexane, add the methyl alcohol of 48～52 times of volumes in the product obtaining, and are heated to 64～66 ℃, stir with this understanding 1.5～2 hours, carry out suction filtration after stirring, obtain filtrate and filter residue after suction filtration;
C, the filtrate that step b is obtained are cooled to room temperature and carry out crystallization, carry out suction filtration after crystallization, obtain cholesterol;
D, the filter residue that step b is obtained add in the mixture of normal hexane and methyl alcohol, and the volume ratio of the mixture of described filter residue and normal hexane and methyl alcohol between the two is 1:10～12, volume ratio 1:1 when described normal hexane and methanol mixed between the two; Then be warming up to 40 ℃～45 ℃, under this temperature condition, stir 1～1.5 hour; After stirring, gained liquid distills under vacuum tightness 0.09MPa, 10～15 ℃ of conditions, is distilled to 30～35% of primary liquid volume; Then decrease temperature crystalline, carries out suction filtration after crystallization, finally obtains high purity product 7-DHC.
According to the separation purification method of above-mentioned 7-DHC, after stirring described in step b, carry out suction filtration, during its suction filtration, vacuum tightness is that 0.09MPa, temperature are 15～20 ℃.
According to the separation purification method of above-mentioned 7-DHC, crystallization time during crystallization described in step c is 12～14h.
According to the separation purification method of above-mentioned 7-DHC, vacuum tightness is that 0.09MPa, temperature are normal temperature during suction filtration described in step c.
According to the separation purification method of above-mentioned 7-DHC, the volume ratio of the mixture of filter residue described in steps d and normal hexane and methyl alcohol between the two is 1:10.
According to the separation purification method of above-mentioned 7-DHC, decrease temperature crystalline described in steps d carries out crystallization 5～6 hours for being cooled to 0 ℃; After described crystallization, carry out suction filtration, during suction filtration, vacuum tightness is that 0.09 MPa, temperature are 0 ℃.
According to the separation purification method of above-mentioned 7-DHC, the purity of the 7-DHC of high purity product described in steps d is greater than 98%.
positive beneficial effect of the present invention:
1, utilize technical solution of the present invention can be effectively from product 7-DHC fermented material separating-purifying go out 7-DHC, and can the unconverted cholesterol of efficient recovery, it is reused for again feeds intake, thereby its raw material is utilized greatly, meet the demand of current sustainable economic development.
2, utilize technical solution of the present invention can access the 7-DHC product that purity is greater than 98%, meet better the market requirement higher to its product purity.
3, adopt at present chemical method to produce in 7-DHC technological process and will use 8 kinds of poisonous and hazardous organic solvents, and the raw material of separating-purifying of the present invention is to adopt biotransformation method synthetic, and only in the product separation stage, use a small amount of (being generally two kinds) organic solvent in biotransformation method building-up process.Reduce pollutant emission, protected physical environment, met biological fermentation production trend in the world.
4, the present invention has all made atlas analysis to the 7-DHC standard substance of selling on market and products obtained therefrom of the present invention, and by analysis: standard substance purity is 92%, product purity of the present invention is that 98.24%(refers to accompanying drawing 1,2).
accompanying drawing explanation:
The liquid-phase chromatographic analysis figure of Fig. 1 7-DHC standard substance;
The liquid-phase chromatographic analysis figure of Fig. 2 product 7-DHC of the present invention.
embodiment:
Below in conjunction with embodiment, further set forth the present invention, but do not limit content of the present invention.
Embodiment 1:
The separation purification method of 7-DHC of the present invention, the detailed step of this separation purification method is as follows:
A, utilize existing cholesterol bio-transformation synthetic method to obtain 7-DHC fermented material in contain microzyme culture medium, unconverted raw material cholesterol and 7-DHC; First gained 7-DHC fermented material is dissolved in solvent normal hexane, and adds water, the add-on of described normal hexane and water is 8 times of 7-DHC fermented material volume, stirs at normal temperatures 1.2h after adding normal hexane and water; After stirring, filter, remove water insoluble and impurity normal hexane; Gained filtrate stratification, then carries out separatory, separates water and organic phase; After separatory, adopt normal hexane washing gained water 3 times, merge organic phase;
B, the organic phase that step a is obtained are distilled, except desolventizing normal hexane, in the product obtaining, add the methyl alcohol of 50 times of volumes, be heated to 65 ℃, stir with this understanding 1.8 hours, after stirring, carry out suction filtration, during suction filtration, vacuum tightness is that 0.09MPa, temperature are 20 ℃, obtains filtrate and filter residue after suction filtration;
C, the filtrate that step b is obtained are cooled to room temperature and carry out crystallization 12h, carry out suction filtration after crystallization, and during suction filtration, vacuum tightness is that 0.09MPa, temperature are normal temperature, obtains cholesterol;
D, the filter residue that step b is obtained add in the mixture of normal hexane and methyl alcohol, and the volume ratio of the mixture of described filter residue and normal hexane and methyl alcohol between the two is 1:10, volume ratio 1:1 when described normal hexane and methanol mixed between the two; Then be warming up to 45 ℃, under this temperature condition, stir 1 hour; After stirring, gained liquid distills under vacuum tightness 0.09MPa, 15 ℃ of conditions, is distilled to 33% of primary liquid volume; Then be cooled to 0 ℃ and carry out crystallization 5 hours, carry out suction filtration after crystallization, during suction filtration, vacuum tightness is that 0.09 MPa, temperature are 0 ℃, finally obtains high purity product 7-DHC (products obtained therefrom purity is 98.24%, refers to accompanying drawing 2).
Embodiment 2:
The separation purification method of 7-DHC of the present invention, the detailed step of this separation purification method is as follows:
A, utilize existing cholesterol bio-transformation synthetic method to obtain 7-DHC fermented material in contain microzyme culture medium, unconverted raw material cholesterol and 7-DHC; First gained 7-DHC fermented material is dissolved in solvent normal hexane, and adds water, the add-on of described normal hexane and water is 10 times of 7-DHC fermented material volume, stirs at normal temperatures 1h after adding normal hexane and water; After stirring, filter, remove water insoluble and impurity normal hexane; Gained filtrate stratification, then carries out separatory, separates water and organic phase; After separatory, adopt normal hexane washing gained water 2 times, merge organic phase;
B, the organic phase that step a is obtained are distilled, except desolventizing normal hexane, in the product obtaining, add the methyl alcohol of 48 times of volumes, be heated to 64 ℃, stir with this understanding 2.0 hours, after stirring, carry out suction filtration, during suction filtration, vacuum tightness is that 0.09MPa, temperature are 18 ℃, obtains filtrate and filter residue after suction filtration;
C, the filtrate that step b is obtained are cooled to room temperature and carry out crystallization 13h, carry out suction filtration after crystallization, and during suction filtration, vacuum tightness is that 0.09MPa, temperature are normal temperature, obtains cholesterol;
D, the filter residue that step b is obtained add in the mixture of normal hexane and methyl alcohol, and the volume ratio of the mixture of described filter residue and normal hexane and methyl alcohol between the two is 1:11, volume ratio 1:1 when described normal hexane and methanol mixed between the two; Then be warming up to 40 ℃, under this temperature condition, stir 1.5 hours; After stirring, gained liquid distills under vacuum tightness 0.09MPa, 10 ℃ of conditions, is distilled to 30% of primary liquid volume; Then be cooled to 0 ℃ and carry out crystallization 6 hours, carry out suction filtration after crystallization, during suction filtration, vacuum tightness is that 0.09 MPa, temperature are 0 ℃, finally obtains high purity product 7-DHC.
Embodiment 3:
The separation purification method of 7-DHC of the present invention, the detailed step of this separation purification method is as follows:
A, utilize existing cholesterol bio-transformation synthetic method to obtain 7-DHC fermented material in contain microzyme culture medium, unconverted raw material cholesterol and 7-DHC; First gained 7-DHC fermented material is dissolved in solvent normal hexane, and adds water, the add-on of described normal hexane and water is 5 times of 7-DHC fermented material volume, stirs at normal temperatures 1.5h after adding normal hexane and water; After stirring, filter, remove water insoluble and impurity normal hexane; Gained filtrate stratification, then carries out separatory, separates water and organic phase; After separatory, adopt normal hexane washing gained water 3 times, merge organic phase;
B, the organic phase that step a is obtained are distilled, except desolventizing normal hexane, in the product obtaining, add the methyl alcohol of 50 times of volumes, be heated to 66 ℃, stir with this understanding 1.5 hours, after stirring, carry out suction filtration, during suction filtration, vacuum tightness is that 0.09MPa, temperature are 15 ℃, obtains filtrate and filter residue after suction filtration;
C, the filtrate that step b is obtained are cooled to room temperature and carry out crystallization 14h, carry out suction filtration after crystallization, and during suction filtration, vacuum tightness is that 0.09MPa, temperature are normal temperature, obtains cholesterol;
D, the filter residue that step b is obtained add in the mixture of normal hexane and methyl alcohol, and the volume ratio of the mixture of described filter residue and normal hexane and methyl alcohol between the two is 1:12, volume ratio 1:1 when described normal hexane and methanol mixed between the two; Then be warming up to 43 ℃, under this temperature condition, stir 1.2 hours; After stirring, gained liquid distills under vacuum tightness 0.09MPa, 15 ℃ of conditions, is distilled to 35% of primary liquid volume; Then be cooled to 0 ℃ and carry out crystallization 5 hours, carry out suction filtration after crystallization, during suction filtration, vacuum tightness is that 0.09 MPa, temperature are 0 ℃, finally obtains high purity product 7-DHC.
Claims (7)
1. a separation purification method for 7-DHC, is characterized in that, described separation purification method comprises the following steps:
A, utilize existing cholesterol bio-transformation synthetic method to obtain 7-DHC fermented material in contain microzyme culture medium, unconverted raw material cholesterol and 7-DHC; First gained 7-DHC fermented material is dissolved in solvent normal hexane, and adds water, the add-on of described normal hexane and water is 5～10 times of 7-DHC fermented material volume, stirs at normal temperatures 1～1.5h after adding normal hexane and water; After stirring, filter, remove water insoluble and impurity normal hexane; Gained filtrate stratification, then carries out separatory, separates water and organic phase; After separatory, adopt normal hexane washing gained water 2～3 times, merge organic phase;
B, the organic phase that step a is obtained are distilled, and except desolventizing normal hexane, add the methyl alcohol of 48～52 times of volumes in the product obtaining, and are heated to 64～66 ℃, stir with this understanding 1.5～2 hours, carry out suction filtration after stirring, obtain filtrate and filter residue after suction filtration;
C, the filtrate that step b is obtained are cooled to room temperature and carry out crystallization, carry out suction filtration after crystallization, obtain cholesterol;
D, the filter residue that step b is obtained add in the mixture of normal hexane and methyl alcohol, and the volume ratio of the mixture of described filter residue and normal hexane and methyl alcohol between the two is 1:10～12, volume ratio 1:1 when described normal hexane and methanol mixed between the two; Then be warming up to 40 ℃～45 ℃, under this temperature condition, stir 1～1.5 hour; After stirring, gained liquid distills under vacuum tightness 0.09MPa, 10～15 ℃ of conditions, is distilled to 30～35% of primary liquid volume; Then decrease temperature crystalline, carries out suction filtration after crystallization, finally obtains high purity product 7-DHC.
2. the separation purification method of 7-DHC according to claim 1, is characterized in that: after stirring described in step b, carry out suction filtration, during its suction filtration, vacuum tightness is that 0.09MPa, temperature are 15～20 ℃.
3. the separation purification method of 7-DHC according to claim 1, is characterized in that: crystallization time during crystallization described in step c is 12～14h.
4. the separation purification method of 7-DHC according to claim 1, is characterized in that: described in step c, vacuum tightness is that 0.09MPa, temperature are normal temperature during suction filtration.
5. the separation purification method of 7-DHC according to claim 1, is characterized in that: the volume ratio of the mixture of filter residue described in steps d and normal hexane and methyl alcohol between the two is 1:10.
6. the separation purification method of 7-DHC according to claim 1, is characterized in that: decrease temperature crystalline described in steps d carries out crystallization 5～6 hours for being cooled to 0 ℃; After described crystallization, carry out suction filtration, during suction filtration, vacuum tightness is that 0.09 MPa, temperature are 0 ℃.
7. the separation purification method of 7-DHC according to claim 1, is characterized in that: the purity of the 7-DHC of high purity product described in steps d is greater than 98%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020104353A1 (en) * | 2018-11-19 | 2020-05-28 | Dsm Ip Assets B.V. | 7-dehydrocholesterol-hemimethanolate |
| CN112979738A (en) * | 2021-03-02 | 2021-06-18 | 浙江新和成股份有限公司 | Crystallization purification method of 7-dehydrocholesterol and application thereof in VD3 production |
| CN115397832A (en) * | 2020-04-23 | 2022-11-25 | 帝斯曼知识产权资产管理有限公司 | Nanofiltration of organic solvents with 7-dehydrocholesterol or 25-hydroxy-7-dehydrocholesterol or OH protected forms thereof |
| CN115746075A (en) * | 2022-10-14 | 2023-03-07 | 浙江新和成股份有限公司 | Method for recovering and purifying 7-dehydrocholesterol in high-impurity-content photochemical reaction liquid in vitamin D3 production process |
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| CN102702295A (en) * | 2012-05-24 | 2012-10-03 | 河南利伟生物药业股份有限公司 | Preparation method of 7-dehydrocholesterol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020104353A1 (en) * | 2018-11-19 | 2020-05-28 | Dsm Ip Assets B.V. | 7-dehydrocholesterol-hemimethanolate |
| CN113015739A (en) * | 2018-11-19 | 2021-06-22 | 帝斯曼知识产权资产管理有限公司 | 7-dehydrocholesterol-hemimethanolic compounds |
| CN115397832A (en) * | 2020-04-23 | 2022-11-25 | 帝斯曼知识产权资产管理有限公司 | Nanofiltration of organic solvents with 7-dehydrocholesterol or 25-hydroxy-7-dehydrocholesterol or OH protected forms thereof |
| CN112979738A (en) * | 2021-03-02 | 2021-06-18 | 浙江新和成股份有限公司 | Crystallization purification method of 7-dehydrocholesterol and application thereof in VD3 production |
| CN112979738B (en) * | 2021-03-02 | 2022-04-05 | 浙江新和成股份有限公司 | Crystallization purification method of 7-dehydrocholesterol and application thereof in VD3 production |
| CN115746075A (en) * | 2022-10-14 | 2023-03-07 | 浙江新和成股份有限公司 | Method for recovering and purifying 7-dehydrocholesterol in high-impurity-content photochemical reaction liquid in vitamin D3 production process |
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Denomination of invention: A Method for Separation and Purification of 7-Dehydrocholesterol Effective date of registration: 20221109 Granted publication date: 20160106 Pledgee: Wenxian Rural Credit Cooperative Association Renmin Road Credit Cooperative Pledgor: Henan Liwei Biological Pharmaceutical Co.,Ltd. Registration number: Y2022980021218 |